CN115233071B - Ni-Fe-based high-temperature medium-entropy alloy and preparation method thereof - Google Patents
Ni-Fe-based high-temperature medium-entropy alloy and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 132
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 131
- 229910003271 Ni-Fe Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 33
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 26
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 24
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 16
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 10
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 10
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 10
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 29
- 238000003723 Smelting Methods 0.000 claims description 22
- 238000005097 cold rolling Methods 0.000 claims description 15
- 238000000137 annealing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000011573 trace mineral Substances 0.000 abstract description 5
- 235000013619 trace mineral Nutrition 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 15
- 238000005728 strengthening Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 238000005275 alloying Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000005496 eutectics Effects 0.000 description 4
- 230000000930 thermomechanical effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a Ni-Fe-based high-temperature medium-entropy alloy and a preparation method thereof, and relates to the technical field of metal materials, wherein the alloy comprises ：Al：6-16.5at％,Cr：6-12at％,Fe：6-15at％,Ni：55-70at％,Mo：0-3at％,W：0-2at％,Nb：0-2at％,Zr：0-1at％,Hf：0-1at％,B：0-0.2at％,Ta：0-1at％,Re：0-2at％; of the following components in percentage by mole, and the Ni/Al ratio is 3.4-10:1; the invention determines the influence rule of trace elements on the high-temperature performance of the Ni-Fe-based FCC/B2 alloy, and the alloy simultaneously shows excellent high-temperature mechanical performance under the condition of ensuring the room-temperature strong plasticity.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a Ni-Fe-based high-temperature medium-entropy alloy and a preparation method thereof.
Background
High-performance superalloys serve as important structural materials and serve an irreplaceable role in a variety of industrial scenes. The high-temperature strength and plasticity of the high-temperature alloy are the main manifestations of mechanical properties, so that the improvement of the high-temperature strength and plasticity is a main target of alloy design on the premise of ensuring certain room-temperature strong plasticity and workability. The medium entropy alloy is used as an emerging alloy concept in recent years, 2-3 main elements are used as a matrix, and the medium entropy alloy has a wide component design space. Compared with the traditional high-temperature alloy, the medium-entropy alloy is widely considered as a promising high-temperature structural material due to the advantages of high mixing entropy, low diffusion coefficient, high strength, high hardness, high wear resistance, high corrosion resistance and the like.
Among the various types of medium entropy alloys, ni—fe based FCC type medium entropy alloys have high damage tolerance, excellent plasticity and wear resistance, but their low high temperature strength limits their application under extreme conditions. Therefore, strengthening the high temperature performance of Ni-Fe based FCC type medium entropy alloys is the primary work of the present invention.
Disclosure of Invention
In order to solve the problems, the invention provides a Ni-Fe-based high-temperature medium-entropy alloy and a preparation method thereof, and aims at the problem of insufficient high-temperature strength of the traditional Ni-Fe-based FCC medium-entropy alloy, and by researching the relationship of elements, tissues and performances, a multi-layer reinforced structure of defects of FCC/B2→crystal grains→FCC/L1 2 →points/lines/surfaces is established, so that the high-temperature strength and plasticity of the alloy are comprehensively improved; by researching the influence of different types of trace alloy elements with different contents on high-temperature performance, the high-temperature plasticity of the Ni-Fe-based high-temperature medium-entropy alloy is improved.
The invention provides a Ni-Fe-based high-temperature medium-entropy alloy, which consists of ：Al：6-16.5at％,Cr：6-12at％,Fe：6-15at％,Ni：55-70at％,Mo：0-3at％,W：0-2at％,Nb：0-2at％,Zr：0-1at％,Hf：0-1at％,B：0-0.2at％,Ta：0-1at％,Re：0-2at％; of the following components in percentage by mole, wherein the Ni/Al ratio is 3.4-10:1;
preferably, the composition ：Al：6-16at％,Cr：9-11at％,Fe：9-12at％,Ni：58-63at％,Mo：0-3at％,W：0-2at％,Nb：0-2at％,Zr：0-1at％,Hf：0-1at％,B：0-0.2at％,Ta：0-1at％,Re：0-2at％;Ni/Al is 3.4-10:1 by mole percent of the following components.
The invention also provides a preparation method of the Ni-Fe-based high-temperature medium-entropy alloy, which comprises the following steps:
Under the inert atmosphere condition, the alloy component Al, cr, fe, ni, mo, W, zr, nb, hf, B, ta, re raw materials which are weighed according to the mole percentage of the elements are smelted for a plurality of times in a vacuum induction smelting furnace or a vacuum arc smelting furnace. After smelting is completed and thoroughly cooled, an alloy ingot is obtained; then casting the alloy melt into a mould to obtain an as-cast intermediate entropy alloy ingot;
And (3) cold rolling the as-cast intermediate entropy alloy ingot, then annealing at 1100-1250 ℃, repeating the cold rolling and annealing processes for a plurality of times, and finally preserving heat at 650-700 ℃ to obtain the Ni-Fe-based high-temperature intermediate entropy alloy.
Preferably, the temperature during smelting is 1500-1650 ℃.
Preferably, the total deformation of the cold rolled thickness is 15% -60%.
Preferably, the heat preservation time of each annealing is 1-30min.
Preferably, the temperature is kept at 650-700 ℃ for 2-12h.
Preferably, the alloy may be further sub-cooled before the heat preservation at 650-700 ℃, and the thickness deformation amount of the cold rolling is 0-30%.
Compared with the prior art, the invention has the following beneficial effects:
The invention improves the high temperature strength of the entropy alloy in the FCC base through the synergistic effect of the following aspects:
In terms of high temperature strength, a B2 phase and an L1 2 phase are introduced into the alloy: the L1 2 phase can improve the high-temperature strength and high-temperature stability of the alloy material, and the introduction of the L1 2 phase into the alloy applied at high temperature can greatly improve the high-temperature strength of the alloy while ensuring the room-temperature strength; the B2 phase can ensure that the alloy has higher yield strength at room temperature;
(1) By adjusting the proportion of Ni and Al, the change of the composition of the as-cast alloy phase is realized. The increase in Ni promotes FCC phase formation, while lower levels favor B2 phase formation. The Ni element is used for stabilizing the FCC phase, so that the high-temperature performance of the medium-entropy alloy can be improved;
(2) The Al element is critical to the formation of the L1 2 phase, and excessive aluminum element can promote the formation of the B2 phase; the invention limits the atomic percentage of Al element to 6-16.5at%, and limits the Ni/Al ratio to 3.4-10:1, and the proper Ni/Al ratio is beneficial to promoting the formation of L1 2 phase (see comparative examples 2-3 in specific examples);
(3) The trace elements can play roles of solid solution strengthening, precipitation strengthening, grain boundary strengthening and the like, and the room temperature and high temperature mechanical properties of the alloy are obviously improved, and the W, mo, B, zr, hf, ta, nb, re and other trace elements are added to obtain higher high temperature strength; wherein, W, mo and Nb elements can cause larger lattice distortion and play a role of solid solution strengthening (the performance improvement is shown in specific examples, examples 1-6, 16-18 and comparative example 1); zr and B elements can strengthen grain boundaries, improve the high-temperature performance of the alloy and eliminate the medium-temperature brittleness of the alloy to a certain extent (see specific examples, examples 7-12 and comparative example 1); hf. Ta and Re elements can promote the generation of an L1 2 precipitated phase in the alloy and play a role in precipitation strengthening (see specific examples, examples 13-15, 19-24 and comparative example 1);
(4) The thermal mechanical processing has important significance in eliminating alloy defects, improving the uniformity of components and tissues, promoting the formation of precipitated phases and the like; through rolling and annealing, casting defects such as shrinkage porosity and macrosegregation in the casting process can be eliminated, the grain structure is thinned, and meanwhile, the formation of an L1 2 nanometer precipitated phase is promoted, which is favorable for the promotion of alloy temperature and high-temperature strong plasticity.
The alloy has high-temperature yield strength which is higher than 650MPa at 800 ℃, and meanwhile, the high-performance high-temperature medium-entropy alloy has excellent room-temperature plasticity and workability, the room-temperature yield strength is about 850MPa, the elongation is 15%, and the high-work hardening rate is realized, so that the design targets of easy processing at room temperature, strength improvement after cold deformation and excellent strength at high temperature are realized, and the high-performance high-temperature medium-entropy alloy with both room-temperature strength and high-temperature strength is obtained.
Drawings
FIG. 1 is a SEM macroscopic microstructure of the entropy alloy of example 13;
FIG. 2 is an SEM microstructure map of an entropy alloy of example 13;
FIG. 3 is a TEM dark field image of the entropy alloy of example 13;
FIG. 4 shows selected area electron diffraction spots at the phase L1 2 of FIG. 3;
fig. 5 the stress strain curves at 800 c for example 13 and 3 comparative examples.
Detailed Description
The present invention will be described in detail below with reference to the drawings and the detailed description, so that those skilled in the art can better understand the present invention and can practice the same, but the examples are not limiting of the present invention.
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Al：6-16.5at％,Cr：6-12at％,Fe：6-15at％,Ni：55-70at％,Mo：0-3at％,W：0-2at％,Nb：0-2at％,Zr：0-1at％,Hf：0-1at％,B：0-0.2at％,Ta：0-1at％,Re：0-2at％; And Ni/Al is 3.4-10:1.
The preparation method of the Ni-Fe-based high-temperature medium-entropy alloy comprises the following steps:
Under the inert atmosphere condition, smelting the alloy component Al, cr, fe, ni, mo, W, zr, nb, hf, B, ta, re raw materials which are weighed according to the mole percentage of elements for multiple times in a vacuum induction smelting furnace or a vacuum arc smelting furnace, and obtaining an alloy ingot after smelting is completed and thoroughly cooled; then casting the alloy melt into a mould to obtain an as-cast intermediate entropy alloy ingot; the smelting temperature is 1500-1650 ℃;
And (3) cold rolling the as-cast intermediate entropy alloy ingot, then annealing at 1100-1250 ℃ for 1-30min, repeating the cold rolling and annealing processes for a plurality of times, wherein the total deformation of the cold rolling thickness is 15-60%, and finally preserving heat at 650-700 ℃ for 2-12h to obtain the Ni-Fe-based high-temperature intermediate entropy alloy. The alloy can be further subjected to cold rolling before heat preservation at 650-700 ℃, and the thickness deformation of the cold rolling is 0-30%.
Al, cr, fe and Ni raw materials used in the following examples were all industrial grade raw materials. Examples 2 to 24 and comparative examples 1 to 3 were the same as the process of example 1, except for the differences in the components, and therefore the process steps were omitted.
Example 1
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole: ni:62.50at%, cr:10.00at%, fe:10.00at%, al:16.50at%, mo:1.00at%, ni/al=3.8.
A method for thermomechanical treatment of Ni-Fe-based high temperature medium entropy alloys comprising the steps of:
S1, ultrasonic cleaning: removing oxide skin on the surface of elements from Ni, cr, fe, al, mo alloy raw materials by using a mechanical grinding method, then placing the alloy raw materials in different containers, adding alcohol solution, ultrasonically cleaning, taking out, and drying alcohol to obtain raw materials after ultrasonic treatment;
s2, proportioning: respectively weighing and mixing the raw materials in S1 according to the mole percentage of the elements;
s3, smelting: putting the mixed raw materials of S2 into a crucible of a vacuum non-consumable arc furnace, closing a furnace door, vacuumizing to 3X 10 -3 Pa, and then backflushing high-purity argon to 0.06MPa; after arcing, firstly smelting a titanium ingot to absorb residual oxygen in a furnace, then smelting the mixed raw materials in the step S2, and simultaneously starting electromagnetic stirring, wherein the smelting current is 190A, the stirring current is 0.5A, the smelting temperature is 1600 ℃, and the smelting time is 2min; after the sample is smelted and thoroughly cooled, turning the sample, repeatedly smelting for 6 times, and keeping the alloy in a liquid state for 2 minutes each time to ensure that the elements are uniformly mixed, and casting an alloy melt into a die after the smelting is finished to obtain an as-cast Ni-Fe-based high-temperature medium-entropy alloy ingot;
S4, after the cold rolling thickness deformation of the intermediate entropy alloy ingot is about 15%, preserving heat at 1200 ℃ for 20min, and then cooling to obtain the intermediate entropy alloy ingot subjected to the first heat mechanical treatment;
The intermediate-entropy alloy ingot subjected to the first thermal mechanical treatment is subjected to secondary cooling for 20 minutes at 1200 ℃ after the thickness deformation amount is about 15%, and then is cooled, so that the intermediate-entropy alloy ingot subjected to the second thermal mechanical treatment is obtained;
the intermediate-entropy alloy ingot subjected to the second thermo-mechanical treatment is subjected to heat preservation at 1200 ℃ for 20min after being subjected to the second-time thermo-mechanical treatment, and then is cooled, so that an intermediate-entropy alloy ingot subjected to the third-time thermo-mechanical treatment is obtained;
The intermediate-entropy alloy ingot subjected to the third thermal mechanical treatment is subjected to secondary cooling, the temperature is kept at 1200 ℃ for 20min after the thickness deformation amount is about 15%, and then cooling is carried out, so that the intermediate-entropy alloy ingot subjected to the fourth thermal mechanical treatment is obtained;
and (3) preserving the heat of the intermediate entropy alloy ingot subjected to the fourth thermal mechanical treatment at 700 ℃ for 120min, and then cooling to obtain the high-performance nickel-iron high-temperature-based intermediate entropy alloy subjected to the thermal mechanical treatment.
Example 2
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.50at％，Cr：10.00at％，Fe：10.00at％，Al：16.50at％，Mo：2.00at％，Ni/Al＝3.7。
Example 3
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：60.50at％，Cr：10.00at％，Fe：10.00at％，Al：16.50at％，Mo：3.00at％，Ni/Al＝3.67。
Example 4
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：62.50at％，Cr：10.00at％，Fe：10.00at％，Al：16.50at％，W：1.00at％，Ni/Al＝3.8。
Example 5
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.50at％，Cr：10.00at％，Fe：10.00at％，Al：16.50at％，W：2.00at％，Ni/Al＝3.7。
Example 6
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：60.50at％，Cr：10.00at％，Fe：10.00at％，Al：16.50at％，W：3.00at％，Ni/Al＝3.67。
example 7
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.49at％，Cr：10.00at％，Fe：10.00at％，Al：16.50at％，Mo：2.00at％，Zr：0.01at％，Ni/Al＝3.7。
Example 8
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.47at％，Cr：10.00at％，Fe：10.00at％，Al：16.50at％，Mo：2.00at％，Zr：0.03at％，Ni/Al＝3.7。
example 9
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.45at％，Cr：10.00at％，Fe：10.00at％，Al：16.50at％，Mo：2.00at％，Zr：0.05at％，Ni/Al＝3.7。
example 10
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.50at％，Cr：10.00at％，Fe：10.00at％，Al：16.50at％，Mo：2.00at％，Zr：0.03at％，B：0.025at％，Ni/Al＝3.7。
Example 11
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.50at％，Cr：10.00at％，Fe：10.00at％，Al：16.50at％，Mo：2.00at％，Zr：0.03at％，B：0.05at％，Ni/Al＝3.7。
example 12
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.50at％，Cr：10.00at％，Fe：10.00at％，Al：16.50at％，Mo：2.00at％，Zr：0.03at％，B：0.075at％，Ni/Al＝3.7。
example 13
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.45at％,Cr：10.00at％,Fe：10.00at％,Al：16.50at％,Mo：2.00at％,Zr：0.03at％,B：0.025at％,Hf：0.05at％,Ni/Al＝3.7.
example 14
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.40at％,Cr：10.00at％,Fe：10.00at％,Al：16.50at％,Mo：2.00at％,Zr：0.03at％,B：0.025at％,Hf：0.10at％,Ni/Al＝3.7.
Example 15
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.35at％,Cr：10.00at％,Fe：10.00at％,Al：16.50at％,Mo：2.00at％,Zr：0.03at％,B：0.025at％,Hf：0.15at％,Ni/Al＝3.7.
Example 16
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.45at％,Cr：10.00at％,Fe：10.00at％,Al：16.50at％,Mo：2.00at％,Zr：0.03at％,B：0.025at％,Nb：0.05at％,Ni/Al＝3.7.
Example 17
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.40at％,Cr：10.00at％,Fe：10.00at％,Al：16.50at％,Mo：2.00at％,Zr：0.03at％,B：0.025at％,Nb：0.10at％,Ni/Al＝3.7.
Example 18
A Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole ：Ni：61.35at％,Cr：10.00at％,Fe：10.00at％,Al：16.50at％,Mo：2.00at％,Zr：0.03at％,B：0.025at％,Nb：0.15at％,Ni/Al＝3.7.
Example 19
A Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole ：Ni：61.45at％,Cr：10.00at％,Fe：10.00at％,Al：16.50at％,Mo：2.00at％,Zr：0.03at％,B：0.025at％,Ta：0.05at％,Ni/Al＝3.7.
Example 20
A Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole ：Ni：61.40at％,Cr：10.00at％,Fe：10.00at％,Al：16.50at％,Mo：2.00at％,Zr：0.03at％,B：0.025at％,Ta：0.10at％,Ni/Al＝3.7.
Example 21
A Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole ：Ni：61.35at％,Cr：10.00at％,Fe：10.00at％,Al：16.50at％,Mo：2.00at％,Zr：0.03at％,B：0.025at％,Ta：0.15at％,Ni/Al＝3.7.
Example 22
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.45at％,Cr：10.00at％,Fe：10.00at％,Al：16.50at％,Mo：2.00at％,Zr：0.03at％,B：0.025at％,Re：0.05at％,Ni/Al＝3.7.
Example 23
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.40at％,Cr：10.00at％,Fe：10.00at％,Al：16.50at％,Mo：2.00at％,Zr：0.03at％,B：0.025at％,Re：0.10at％,Ni/Al＝3.7.
Example 24
The Ni-Fe-based high-temperature medium-entropy alloy consists of the following components in percentage by mole:
Ni：61.35at％,Cr：10.00at％,Fe：10.00at％,Al：16.50at％,Mo：2.00at％,Zr：0.03at％,B：0.025at％,Re：0.15at％,Ni/Al＝3.7.
Comparative examples 1-3 are intended to be compared with example 13, which is the best performing, and to highlight the effect of trace alloying elements on both high temperature strength and plasticity of the alloy, as shown in fig. 5. Comparative example 1 is a high temperature medium entropy alloy matrix without trace alloying elements added, comparative example 2 is a Ni 30Co30Cr10Fe10Al18W2 eutectic high entropy alloy, and comparative example 3 is an AlCoCrFeNi 2.1 eutectic high entropy alloy. It can be seen that the yield strength at 800 ℃ is much higher for example 13 than for the three comparative examples. The trace element alloying can realize very high temperature strength under the condition of ensuring plasticity. Therefore, the design thought of the high-temperature medium-entropy alloy in the patent is effective and feasible.
Comparative example 1
The medium entropy alloy consists of the following components in percentage by mole: ni:63.50at%, cr:10.00at%, fe:10.00at%, al:16.50at%, ni/al=3.8.
Comparative example 2
The Ni 30Co30Cr10Fe10Al18W2 eutectic high-entropy alloy consists of the following components in percentage by mole: ni:30.00at%, co:30.00at%, cr:10.00at%, fe:10.00at%, al:18.00at%, W:2.00at%, ni/al=1.7.
Comparative example 3
The AlCoCrFeNi 2.1 eutectic high-entropy alloy consists of the following components in percentage by mole: ni:34.43at%, co:16.39at%, cr:16.39at%, fe:16.39at%, al:16.39at%; ni/al=2.1.
Table 1 adjusting the Performance index of the trace element species and content sample example
TABLE 2 composition and actual Performance index of each comparative example
In order to illustrate the microstructure of the high-temperature high-strength medium-entropy alloy provided by the invention, the microstructure characterization is performed on the high-performance nickel-iron-based medium-entropy alloy provided in the embodiment 13, as shown in fig. 1-4. FIG. 1 is a macroscopic microstructure of example 13, showing that the alloy consists of FCC and B2 phases. FIG. 2 is a graph showing the microstructure of example 13 after thermal mechanical treatment, wherein the alloy structure is composed of a fine L1 2 phase distributed in FCC. FIG. 3 is a transmission electron micrograph of example 13 showing a large number of nano-scale L1 2 phases distributed in the alloy. FIG. 4 is a plot of selected electron diffraction spots corresponding to example 13, which is a superlattice diffraction spot of a typical L1 2 phase.
In conclusion, the invention researches the influence rule of adjusting the proportion of Ni and Al and adding a certain trace of alloy elements on the structure and performance of the Ni-Fe-based high-temperature medium-entropy alloy. Studies have shown that the use of a relatively low cost, properly adjusted Ni to Al ratio can induce significant amounts of L1 2 phases in the FCC matrix. Meanwhile, mo, W, zr, B, hf, nb, re and other trace alloying elements have the immediate effects of stabilizing the L1 2 phase, promoting the generation of the L1 2 phase, strengthening interfaces and the like, so that the alloy can greatly improve the high-temperature strength while keeping excellent high-temperature plasticity.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The Ni-Fe-based high-temperature medium-entropy alloy is characterized by comprising the following components in percentage by mole:
Al：6-16.5 at%,Cr：6-12 at%,Fe：6-15 at%,Ni：55-70 at%,Mo：2-3 at%,W：0-2 at%,Nb：0-2 at%,Zr：0.03-0.05 at%,Hf：0-1 at%,B：0-0.2 at%,Ta：0-1 at%,Re：0-2 at%; And Ni/Al is 3.67-3.7:1;
Introducing a B2 phase and an L1 2 phase into the FCC-based entropy alloy, and controlling the Ni/Al ratio to promote the formation of an L1 2 phase;
and (3) cold rolling the as-cast intermediate entropy alloy ingot, then annealing at 1100-1250 ℃, repeating the cold rolling and annealing processes for a plurality of times, and finally preserving heat at 650-700 ℃ to obtain the Ni-Fe-based high-temperature intermediate entropy alloy.
2. The Ni-Fe-based high temperature mid-entropy alloy according to claim 1, consisting of the following components in mole percent ：Al：6-16 at%,Cr：9-11 at%,Fe：9-12 at%,Ni：58-63 at%,Mo：2-3 at%,W：0-2 at%,Nb：0-2 at%,Zr：0.03-0.05 at%,Hf：0-1 at%,B：0-0.2 at%,Ta：0-1 at%,Re：0-2 at%; and Ni/Al 3.67-3.7:1.
3. The method for producing a Ni-Fe-based high temperature medium entropy alloy according to claim 1 or 2, comprising the steps of:
Under the inert atmosphere condition, smelting the alloy component Al, cr, fe, ni, mo, W, zr, nb, hf, B, ta, re raw materials which are weighed according to the mole percentage of elements for multiple times in a vacuum induction smelting furnace or a vacuum arc smelting furnace, and obtaining an alloy ingot after smelting is completed and thoroughly cooled; then casting the alloy melt into a mould to obtain an as-cast intermediate entropy alloy ingot;
And (3) cold rolling the as-cast intermediate entropy alloy ingot, then annealing at 1100-1250 ℃, repeating the cold rolling and annealing processes for a plurality of times, and finally preserving heat at 650-700 ℃ to obtain the Ni-Fe-based high-temperature intermediate entropy alloy.
4. The method for preparing a Ni-Fe-based high-temperature medium-entropy alloy according to claim 3, wherein the temperature during smelting is 1500-1650 ℃.
5. The method for producing a Ni-Fe-based high temperature medium entropy alloy according to claim 3, wherein the total deformation amount of the cold rolled thickness is 15% to 60%.
6. The method for preparing a Ni-Fe-based high temperature medium entropy alloy according to claim 3, wherein the heat preservation time per annealing is 1-30 min.
7. The method for preparing a Ni-Fe-based high temperature medium entropy alloy according to claim 3, wherein the time of heat preservation at 650-700 ℃ is 2-12 h.
8. The method for producing a Ni-Fe-based high temperature medium entropy alloy according to claim 3, wherein the alloy is further subjected to cold rolling before heat preservation at 650-700 ℃ and the thickness deformation amount of the cold rolling is 0-30%.
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